CN105579566B

CN105579566B - Oil extraction aid in grain processing

Info

Publication number: CN105579566B
Application number: CN201480047275.9A
Authority: CN
Inventors: S·R·刘易斯; P·W·夏佩德三世
Original assignee: Solenis Technologies Cayman LP
Current assignee: Solenis Technologies Cayman LP
Priority date: 2013-08-28
Filing date: 2014-08-29
Publication date: 2020-01-10
Anticipated expiration: 2034-08-29
Also published as: CA2919761A1; US9353332B2; WO2015030852A1; US20150184112A1; EP3039106A1; EP3039106B1; AU2014311826A1; CA2919761C; CN105579566A; AU2014311826B2; MX2016002288A

Abstract

Methods are provided for using a processing additive system to improve the separation of oil from a process stream (whole stillage, thin stillage, or syrup) that is a byproduct in the production of ethanol from grain.

Description

Oil extraction aid in grain processing

Technical Field

The invention relates to the recovery of oil in the process of producing ethanol from grains.

Background

There are two types of processes for producing ethanol from grains, wet milling and dry milling. The main difference between these two methods is how they initially treat the grain. In the wet milling process, the grain is soaked in water and then separated in a first step for processing. Dry milling is more common and requires a different process.

Corn dry milling processes, also referred to herein as dry milling processes, for the production of ethanol are well known. For example, see "Corn Milling, Processing and coproduction" by Kelly s.davis, Minnesota Nutrition Conference, Technical seminar, 11 d.2001 (Kelly s.davis, "Corn Milling, Processing and Generation of Co-Products," Minnesota Nutrition Conference, Technical Symposium,11September 2001). Ethanol plants typically process whole stillage from a beer column by centrifugation to produce a wet cake and thin stillage, followed by multi-effect evaporation of the thin stillage to increase solids content and recovery of distillate for return use in the process (figure 1). As the solids content increases, the thin stillage is often referred to as a syrup (see fig. 1). The slurry can be sold as a product, but more typically is combined with a wet cake or distillery dried grain and sold as an animal feed. These processes are well known in the industry and are typically employed in the plant design of the industry.

To utilize the co-product stream, many plants incorporate an oil removal process in which thin stillage or syrup is subjected to such processes as centrifugation or extraction to remove corn oil from the syrup. This corn oil is also known as Distilled Corn Oil (DCO). For example, the use of centrifuges to separate corn oil from a slurry is widely used in the fuel ethanol industry. Although the theoretical oil yield per bushel of processed corn is 1.6 pounds per bushel, many commercial facilities do not achieve this far. Increasing the corn oil production of the plant by 0.1 gallon per minute corresponds to an additional 400,000 pounds of annual oil production. This is a significant source of additional revenue for the plant.

Recently, there have been efforts to improve the value model for ethanol production from corn by extracting oil from thin stillage by-products. U.S. patent No. 7,602,858B 2 describes a mechanical method of separating oil from concentrated thin stillage (referred to as "syrup") using a disk stack centrifuge. U.S. patent application No. 2008/0176298 a1 describes a method for extracting corn oil in an ethanol production process using an alkyl acetate solvent.

A technique of particular interest is that it does not require capital expenditure to implement new mechanical schemes and/or significant process changes, such as the use of solvent extraction techniques that require recovery. U.S. patent application No. 2012/0245370 a1 describes a method of improving the oil extraction process. When using known processes, some oil is still not recovered from the slurry. Therefore, it is possible to further improve the oil recovery process.

Also of particular interest are those using processing additives that have long-term storage stability and are easily pumped and handled.

Disclosure of Invention

A process for improving the separation of oil from a process stream (whole and/or thin stillage and/or syrup) obtained as a byproduct in the production of ethanol from a grain such as corn or wheat is disclosed. The method is to add a process additive system comprising at least one chemical additive and at least one hydrophobic silica to a process stream for producing ethanol from a grain, such as corn or wheat. The process involves treating any process stream downstream of the distillation operation in the production of ethanol from grains with a process additive system that can enhance the mechanical separation of oil from the stream.

Preferably, the process additive system comprises materials that are considered safe so that they do not impair the end use of the resulting distillers dried grains with solubles (DDGS) or wet distillers grains with solubles (WDGS) as feedstock.

In some cases, the present invention may provide the benefits of 1) improved oil production over existing processes; and/or 2) producing cleaner (high quality) oil by reducing suspended solids and/or water content in the resulting oil; and/or 3) reduced maintenance of the centrifuge, reduced down time and cleaning requirements by reducing deposited material, and allowing for extended time between blowback cleaning, resulting in increased throughput and reduced down time, while providing the benefit of simpler and easier cleaning of the centrifuge upon failure; and/or 4) reduced maintenance of the vaporizer, reduced frequency and complexity of cleaning by reducing deposited material, reduced down time, and reduced cost.

Description of the figures

FIG. 1: a partial general overview of corn ethanol production, giving some points of addition of chemical additives: point 1-addition to whole stillage at or near the inlet of centrifuge 1 before separation into wet cake and thin stillage; point 2-at or near the inlet of the evaporator; point 3-direct entry into evaporator; point 4-before or at the inlet of the oil centrifuge, centrifuge 2.

Detailed Description

A process for improving the separation of oil from a process stream (whole stillage and/or thin stillage and/or syrup) obtained as a byproduct in the production of ethanol from grain is disclosed. Corn is the most commonly used grain, but other grains such as wheat, sorghum (sorghum), and barley may also be used. The method includes adding a process additive system including at least one chemical additive and at least one hydrophobic silica to a process stream for producing ethanol from grain, preferably corn. The process involves treating grain, preferably corn, with a processing additive system that can enhance the mechanical separation of oil from the stream, any processing streams downstream of the distillation operation in the production of ethanol.

A method for improving the separation of oil from whole stillage, thin stillage or syrup processing operations in the production of ethanol from grain, preferably corn, preferably using a dry milling process, thereby increasing the yield of oil is disclosed.

The present invention describes a process for recovering oil from the production of ethanol from cereals, preferably corn, comprising the addition of a processing additive system comprising at least one chemical additive and at least one hydrophobic silica having a particle size of more than 0.01 μm or more than 0.1 μm, or more than 0.5 μm, or more than 1 μm and ranging from 3 to 50 wt% based on the total weight of the processing additive system. The amount of the chemical additive is 20% of the process additive system and may be as high as 97% of the process additive system. Useful modifiers are those added to modify the sedimentation stability, rheological properties such as viscosity and thixotropy, and/or elasticity of the processing additive system.

In one aspect of the invention, the method includes applying the process additive system to the thin stillage process stream and/or the slurry concentrate in an oil separation step. Preferably, the separation of the oil from the concentrated slurry is achieved by mechanical operations such as membranes or centrifugation. The separation can be achieved with a centrifuge such as a disk stack or a horizontal tricner centrifuge. Other mechanical separators that may also be used in the present invention include, but are not limited to, reverse phase centrifugal cleaners.

In another aspect of the invention, the method includes applying the process additive system to whole stillage prior to separation into thin stillage and a wet cake.

In another embodiment, the process additive system may also be added to a grain ethanol production process stream through multiple addition points. The processing additive system added at each point need not have the same composition or be added in the same metered amounts, so long as the total amount of each component and the total amount of all points added are within the specified ranges for the processing additive system.

FIG. 1 is a partial general overview of ethanol production from corn. In a typical corn ethanol production process, corn is converted to a material called "beer" after a number of different saccharification and fermentation steps. The beer is then processed by a distillation process to separate out the caide ethanol, leaving a stillage byproduct known as whole stillage. The whole stillage is subjected to a solid separation centrifugation process to obtain wet stillage and thin stillage. The thin stillage is then typically processed through a plurality of evaporator units to obtain a concentrated slurry. The slurry may then be further processed, for example by oil separation centrifugation, to separate oil from the slurry. The remaining pulp is then typically combined with wet distillers grains and dried to yield distillers dried grains with solubles (DDGS). The process additive system of the present invention is typically added to the process stream at various points in the separation process. Figure 1 shows a preferred addition point. The regions where the process additive system is typically added during the process are indicated in the figure by the parenthesized ("{ … }") regions.

The process additive system may also be added at various points in the separation system. The addition point of the process additive system includes, but is not limited to, a whole stillage process stream before separation into a wet cake and thin stillage, a process stream at or near the inlet of the centrifuge, or after a solids separation centrifuge. The process additive system may be added to the slurry just before the oil separation centrifuge and/or at the premix inlet or retention heating tank, and at a point before the slurry feed tank and centrifuge, either in the evaporator before or at the inlet and/or outlet of one or more thin stillage evaporators.

The processing additive systems suitable for use in the present invention can increase oil production. The application of the processing additive may include one or more addition points within the thin stillage processing unit operation. The process additive system may be applied to a slurry resulting from the concentration of thin stillage in an evaporator. The processing additive system suitable for use in the present invention comprises at least two components; chemical additives and hydrophobic silica and optionally modifiers.

The chemical additive is a component of the processing additive system. Such additives suitable for use in the present invention are functionalized polyols derived from sorbitol, sorbitan, isosorbide, sucrose, or glycerin, including 1, 4-sorbose. Preferred chemical additives are functionalized polyols including alkoxylated sorbitan monoalkylates, alkoxylated sorbitan dialkylates, alkoxylated sorbitan trialkylates and mixtures thereof. The alkyl chain length of the alkoxylated alkylate of sorbitan is from 6 to 24 carbon atoms, or about 8 to 18 carbon atoms, preferably the alkoxylated sorbitan alkylate is an alkoxylated sorbitan ester. The alkylate of alkoxylated sorbitan is preferably alkoxylated with about 5 to 100 moles, or 5 to 60 moles, or about 10 to 30 moles, or about 12 to 30, or about 12 to 25 moles of alkyl oxide. Preferably the alkoxylated sorbitan alkylate is an alkoxylated sorbitan ester. Preferred alkyl oxides are ethylene oxide and propylene oxide or combinations thereof. Preferred alkoxylated sorbitan alkylates are sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate or sorbitan monostearate alkoxylated with less than 50 moles or less than 30 moles of ethylene oxide or propylene oxide or combinations thereof. More preferred alkoxylated sorbitan alkylates are sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate or sorbitan monostearate ethoxylated with about 10 to 30 moles of ethylene oxide or propylene oxide or combinations thereof, preferably said alkoxylated sorbitan alkylates are alkoxylated sorbitan esters. More preferably, the alkoxylated sorbitan alkylate is sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate or sorbitan monostearate alkoxylated with about 12 to 25 moles of ethylene oxide or propylene oxide or a combination thereof, and preferably the alkoxylated sorbitan alkylate is an alkoxylated sorbitan ester. It is preferred for the present invention that the composition/class of such materials be or can be classified as safe so that they do not impair the potential end use of the resulting distiller's dried grain as a feedstock.

Other classes of chemical additives useful in the present invention are alkoxylated sorbitan esters, alkoxylated fatty alcohols, alkoxylated fatty acids, sulfonated alkoxylates, alkyl quaternary ammonium compounds, alkylamine compounds, alkylphenol ethoxylates, and mixtures thereof. Other classes of additives useful in the present invention include fatty acid salts (sodium, ammonium or potassium salts) and low molecular weight silicone surfactants. The alkoxylated portion of the foregoing chemical agent may be any mixture of ethylene oxide and propylene oxide added to the base molecule in a block or random fashion. Most preferred are alkoxylated sorbates alkoxylated with about 5 to 100 moles of alkyl oxide, or 5 to 60 moles, or about 10 to 30 moles, or about 12 to 25 moles.

Silicon dioxideIs the second component of the processing additive system. Silicas suitable for use in the present invention are hydrophobic silicas prepared from precipitated silicas, fumed silicas, colloidal silicas, thermal silicas, or silica gels. These synthetic silicas are amorphous. Preferred hydrophobic silicas include hydrophobic precipitated silicas, hydrophobic fumed silicas, and mixtures thereof. Examples of commercially available precipitated hydrophobic silicas include

D-series (Evonik Corporation, Parsippany, NJ), Perform-O-Sil (Performance Process, Inc., Mundelein, IL), and Dumacil (Hi-Mar Specialty Chemicals, LLC, Milwaukee, Wis.) product lines. Examples of commercially available fumed hydrophobic silicas includeR-series (Evonik Corporation, Parsippany, NJ), Profusil (Performance Process, Inc., Mundelein, IL),

TS-series (Cabot corporation, Billerica, MA), and

h-series (Wacker Chemical Corporation, Adrian, MI) product line.

The particle diameter of silica referred to in the present invention means a median particle diameter (d) measured by laser diffraction₅₀)。

It is well known to those skilled in the art that hydrophobic silicas produced are generally present in the form of agglomerates comprising aggregates and primary subunits. Aggregates are defined as primary subunits attached to each other at their surface, which are generally not separable by the dispersion process. Agglomeration is defined as a loose clustering of primary subunits and/or aggregates, which can be separated by dispersion (DIN 53206). Because of the nature of the synthetic silica production process, there is a particle size distribution for a given silica product. A given hydrophobic silica product may consist of an aggregate mixture, non-agglomerated aggregates, and/or non-agglomerated primary subunits. Particle size measurement, as cited above, measures the maximum form of silica present. For example, if three aggregates are non-caking, a particle size measurement will indicate the presence of three particles corresponding to the size of each aggregate. However, if three aggregates are present as one agglomerated particle, the particle size measurement will indicate the presence of one particle having the corresponding agglomerated particle size. Although fumed silica particles are generally smaller than precipitated silica, this is not always the case, as they can form agglomerates larger than 10 μm. Silicas with higher surface areas generally have higher thickening capabilities. It is well known to those skilled in the art that the production process for preparing precipitated and fumed silicas can be adjusted to produce silicas having different particle sizes, specific surface areas, and other properties. It is also well known to those skilled in the art that different methods may be used to de-agglomerate these agglomerates and/or de-agglomerate particle aggregates to obtain the desired particle size and/or particle size distribution. One major difference between pyrogenic and precipitated silicas is the presence of a high density of silanol groups at the surface of the precipitated silica.

Different particle sizes of silica may be used in the present invention. Suitable hydrophobic silica particle sizes include about 0.01-200 μm, about 0.01-100 μm, about 0.01-60 μm, about 0.1-200 μm, about 0.1-100 μm, about 0.1-60 μm, about 0.5-200 μm, about 0.5-100 μm, about 0.5-60 μm, about 1-200 μm, about 1-100 μm, about 1-60 μm.

The hydrophobic silica may be a mixture of silicas of different particle sizes. Different sizes can be mixed to give a processing additive system comprising particles which can be as small as 0.01 μm and as large as 200 μm, as small as 0.05 μm and as large as 200 μm, as small as 0.1 μm and as large as 100 μm, as small as 0.5 μm and as large as 100 μm. For example, silica having a small particle size may be mixed with silica having a large particle size to obtain a silica mixture having a substantially desired particle size.

Furthermore, it may be desirable to adjust the sedimentation stability, rheological properties such as viscosity and thixotropy, and/or elasticity of the processing additive system. Materials suitable for this or other purposes include hydrophobic or hydrophilic silicas of smaller particle size and/or modifiers such as fatty acid alkyl esters, monoglycerides, diglycerides, triglycerides, mineral oils, and alcohols.

Smaller particle size silicas can provide additional benefits for processing additive systems. Typically these smaller particle size silicas range in size from 0.01 to 20 microns. These silicas help control sedimentation stability, rheological properties, and/or elasticity of the processing additive system. The silica may be fumed, precipitated, colloidal, thermal, or gel, and mixtures thereof. Preferred hydrophobic silicas include hydrophobic precipitated silicas, hydrophobic fumed silicas, and compounds thereof. The particle size of the silicas suitable for use in the present invention to control these properties may range from about 0.01 to 20 μm, from about 0.01 to 10 μm, from about 0.01 to 5 μm, from about 0.05 to 20 μm, from about 0.05 to 10 μm, from about 0.05 to 5 μm. Typically the particles are less than 10 μm, or less than 5 μm or less than 3 μm. Typically the particles are greater than 0.01 μm, greater than 0.05 μm. Silica of this size can provide the benefit of increasing the settling stability of the processing additive system and modifying its rheological and/or elastomeric properties. Hydrophilic silica may also be used; it should be noted, however, that the use of such silicas in high concentrations leads to processing additive systems having very high viscosities.

One class of modifiers suitable for adjusting the sedimentation stability, rheological properties and/or elasticity of the process additive system includes a wide variety of mono-, di-, and triglycerides (oils and fats) available from plant and animal sources, which are known in the food, chemical and other industries. These include, but are not limited to, corn, canola, palm kernel, coconut, peanut, soybean, sunflower, and castor oil as well as lard and tallow. In addition, synthetic methods can be used to prepare similar mono-, di-, and triglycerides. Another class of modifiers suitable for modifying these properties are fatty acid alkyl esters, which are the alkyl esters of the aforementioned triglycerides and/or similar fatty acids. Examples include soy methyl ester, erucic acid methyl ester, and soy ethyl ester. Other suitable modifiers include mineral oils and alcohols. These modifiers may generally be added to reduce the viscosity of the processing additive system or to improve its compatibility with the medium to which it is added.

Typically, the amount of chemical additive in the process additive system is from 20 to 97% of the total process additive system, or from 20% to less than 95% of the total process additive system, or from 40% to less than 95% of the total process additive system.

In general, it is advantageous if the total silica concentration in the processing additive system, including all of the silica added to the processing additive system, is from 3 to 50 wt% of the entire processing additive system, or from 3 to 40 wt% of the entire processing additive system, or from 3 to 30 wt% of the entire processing additive system. The concentration in the silica can be from greater than 5% to 50% by weight of the entire processing additive system, from greater than 5% to 40% by weight of the entire processing additive system, from greater than 5% to 30% by weight of the entire processing additive system, wherein the silica content includes all of the silica added to the processing additive system.

If smaller particle size silicas are used to adjust the sedimentation stability, rheological properties, and/or elasticity of the processing additive system for a given end use, they may be used in amounts of about 0.1 to 80 weight percent of the total amount of silica in the processing additive system, about 1 to 80 weight percent of the total amount of silica in the processing additive system, and about 5 to 50 weight percent of the total amount of silica in the processing additive system.

If modifiers such as fatty acid alkyl esters, monoglycerides, diglycerides, triglycerides, mineral oils, and/or alcohols are used to adjust the settling stability, rheological properties, and/or elasticity of the processing additive system for a given end use, they may be used in an amount of about 0.1 to 30 weight percent of the entire processing additive system, about 0.1 to 25 weight percent of the entire processing additive system, and about 1 to 25 weight percent of the entire processing additive system.

The process additive system may be added to a process stream (whole stillage, thin stillage or syrup) for producing ethanol from corn, preferably corn, in an amount of about 20 to 10,000ppm, about 20 to 4000ppm, about 20 to 2000ppm, about 20 to 1500ppm based on the weight of the process stream, about 50 to 10,000ppm, about 50 to 4000ppm, about 50 to 2000ppm, about 50 to 1500ppm based on the weight of the process stream, about 100 to 10,000ppm, about 100 to 4000ppm, about 100 to 2000ppm, about 100 to 1500ppm based on the weight of the process stream.

One embodiment of the invention comprises adding to a grain ethanol production process a composition comprising 20-97% of a chemical additive, 3-50% of a hydrophobic silica, and optionally 0-30% of a modifier, wherein the chemical additive is an alkoxylated sorbitan alkylate, added to the grain ethanol production process stream in an amount of 20-10,000ppm based on the weight of the process stream.

The process additive system can be heated and applied to the process stream (whole stillage, thin stillage or syrup) at a temperature in the range of 18 to 100 ℃, 25 to 85 ℃, 30 to 80 ℃.

A negative effect of processing the slurry at higher temperatures, such as greater than 195 ° F or 205 ° F according to the process, to increase oil yield is discoloration of the resulting slurry, which makes the DDGS less attractive and reduces the value of the material. Higher processing temperatures can cause the oil itself to darken in color. Thus, the present invention has the added benefit of being able to increase oil yield at lower processing temperatures and reduce the likelihood of the processed slurry having a poor appearance and increase the value of the DDGS and oil. Reducing the processing temperature also results in overall energy savings.

Examples

Raw material

The raw materials used in the examples include the following. Polysorbate 80, also known as POE (20) sorbitan monooleate. Polysorbate 40, also known as POE (20) sorbitan monopalmitate. Polysorbate 20, also known as POE (20) sorbitan monolaurate. Hydrophobic silica A is a hydrophobized mixture of about 25% by weight of precipitated silica having a median particle diameter of 9 μm and 75% by weight of precipitated silica having a median particle diameter of 35 μm. The hydrophobic silica B is a precipitated hydrophobic silica having a median particle diameter of about 11 to 13 μm. Hydrophobic silica C is

R812, a BET surface area of 260. + -.30 m²Per gram of fumed hydrophobic silica. Both "pulp" and "corn pulp" refer to the concentrated thin stillage in the production of ethanol from dry-milled corn.

Example 1

Polysorbate 80 and a blend of polysorbate 80 with hydrophobic silica a and methyl soyate were added to the slurry feed line on the pump feed side of the two disk stack centrifuge feed in a corn ethanol production process in a 537ppm dose. The production of the corn oil obtained is shown in table 1. Oil production was increased compared to baseline data obtained with polysorbate 80.

TABLE 1

As shown in table 1, the addition of hydrophobic silica to polysorbate 80 resulted in an increase in oil production. Increasing the concentration of hydrophobic silica from 5 wt% to 9 wt% resulted in additional oil production.

Example 2

Different polysorbates were added to the slurry feed line on the pump feed side of two disk stack centrifuges feeding in a 537ppm dosage during ethanol production from corn. The corn oil yields obtained are shown in table 2.

TABLE 2

As shown in table 2, polysorbate 80 and polysorbate 40 performed similarly.

Example 3

Polysorbate 80 and a blend of polysorbate 80 and hydrophobic silica and fatty acid methyl esters were added to the slurry feed line at the pump feed side of the two disk stack centrifuge feed in the corn ethanol production process in a 271ppm dose. The corn oil yields obtained are shown in table 3. Oil production was increased compared to baseline data obtained with polysorbate 80.

TABLE 3

As shown in table 3, the addition of hydrophobic silica resulted in additional oil production compared to baseline.

Example 4

Polysorbate 80 (additive 1) and a blend of 85 wt% polysorbate 80 with 10 wt% hydrophobic silica and 5 wt% methyl soyate (additive 2) were added to the slurry feed line on the pump feed side of the two disk stack centrifuges fed during ethanol production from corn. The corn oil yields obtained are shown in table 4. Changes in processing additive dosing and changes in oil production were compared to baseline data obtained with polysorbate 80.

TABLE 4

	Additive 1	Additive 2
			Metering (ppm)	692	494
Variation of metering		-29％
			Oil yield (gallons/minute)	2.3	2.3
Variation of oil production		0％

As shown in table 4, the addition of hydrophobic silica to polysorbate 80 resulted in the production of more oil per unit amount of additive than with polysorbate 80 alone.

Example 5

Polysorbate 80 and a blend of polysorbate 80 and methyl soyate were added at a dosage of 626ppm to the slurry feed line on the pump feed side of the two disk stack centrifuge feed in the corn ethanol production process. The corn oil yields obtained are shown in table 5.

TABLE 5

As shown in table 5, the addition of fatty acid methyl esters to polysorbate 80 did not result in a significant decrease in oil production. The viscosity of the fatty acid methyl ester modified processing additive system can be used.

Example 6

The effect of hydrophobic silica content on the efficacy of the processing additive system was investigated. This was tested by adding 700ppm of the process additive system to 35mL of corn syrup at 90 ℃ and then mixing for 0.5 minutes. 10mL of each sample was transferred to a centrifuge tube and then centrifuged at 3000rpm for 10 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube. A control sample without additives was tested for comparison.

TABLE 6

As can be seen from table 6, the addition of hydrophobic silica to polysorbate 80 resulted in a significant increase in oil release compared to polysorbate 80 alone.

Example 7

The effect of hydrophobic silica content on the efficacy of the processing additive system was investigated. This was tested by adding 300ppm of the process additive system to 80mL of corn syrup at 90 ℃ and then mixing briefly. 65mL of each sample was transferred to a centrifuge tube and then centrifuged at 1700rpm for 2 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube.

TABLE 7

As can be seen from table 7, the addition of hydrophobic silica to polysorbate 80 resulted in a significant increase in oil release compared to polysorbate 80 alone.

Example 8

The effect of hydrophobic silica B content on the efficacy of the processing additive system was investigated. This was tested by adding 300ppm of the process additive system to 80mL of corn syrup at 90 ℃ and then mixing briefly. 65mL of each sample was transferred to a centrifuge tube and then centrifuged at 1700rpm for 2 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube.

TABLE 8

As can be seen from table 8, the addition of hydrophobic silica to polysorbate 20 resulted in a significant increase in oil release compared to polysorbate 20 alone.

Example 9

The effect of hydrophobic silica B content on the efficacy of the processing additive system was investigated. This was tested by adding 600ppm of the process additive system to 80mL of corn syrup at 90 ℃ and then mixing briefly. 65mL of each sample was transferred to a centrifuge tube and then centrifuged at 1700rpm for 2 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube.

TABLE 9

As can be seen from table 9, the addition of hydrophobic silica resulted in a significant increase in oil release compared to polysorbate 20 alone.

Example 10

The effect of the particle size of the hydrophobic silica on the efficacy of the processing additive system was investigated. This was tested by adding 300ppm of the process additive system to 80mL of corn syrup at 90 ℃ and then mixing briefly. 65mL of each sample was transferred to a centrifuge tube and then centrifuged at 2000rpm for 15 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube. Median particle size was measured using a Horiba LA-950 laser scattering particle size distribution analyzer (software version 3.29, firmware version 3.5011/28) and fitted with a volume distribution. The sample was dissolved in isopropanol and analyzed with a refractive index of hydrophobic silica of 1.460 and a refractive index of isopropanol of 1.376.

Watch 10

As can be seen from table 20, the addition of hydrophobic silica of different particle size to polysorbate 80 resulted in a significant increase in oil release compared to polysorbate 80 alone.

Example 11

The effect of the particle size of the hydrophobic silica on the efficacy of the processing additive system was investigated. This was tested by adding 700ppm of the process additive system to 35mL of corn syrup at 90 ℃ and then mixing for 0.5 minutes. Subsequently, 10mL of the treated slurry was transferred to a centrifuge tube and centrifuged at 3000rpm for 10 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube.

TABLE 11

As can be seen from table 11, the addition of hydrophobic silica a or B to polysorbate 80 resulted in a significant increase in oil release compared to polysorbate 80 alone.

Example 12

The effect of hydrophobic silica on the efficacy of the processing additive system was examined without the addition of polysorbate 80 (P80). Silica is first dispersed in corn oil to aid in the addition of the processing additive system to the corn syrup. This was tested by adding a specific metered processing additive system to 35mL of corn syrup at 90 ℃ and then mixing for 0.5 minutes. Subsequently, 10mL of the treated slurry was transferred to a centrifuge tube and centrifuged at 3000rpm for 10 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube. All silica was dispersed in corn oil (20 wt% silica and 80 wt% corn oil) before being added to the slurry in the specified amount.

TABLE 12

As can be seen from table 12, the addition of hydrophobic silica alone did not result in a significant increase in oil release. P80 represents polysorbate 80.

Example 13

The effect of the addition of fatty acid methyl esters (soybean fatty acid methyl esters) on the efficacy of the processing additive system was examined. This was tested by adding 700ppm of the process additive system to 35mL of corn syrup at 90 ℃ and then mixing for 0.5 minutes. Subsequently, 10mL of the treated slurry was transferred to a centrifuge tube and centrifuged at 3000rpm for 10 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube.

Watch 13

As can be seen from table 13, the addition of fatty acid methyl esters has no significant adverse effect on the performance of the silica containing processing additive system.

Example 14

The effect of the type of fatty acid methyl ester addition (soy and methyl erucate) on the efficacy of the processing additive system was examined. This was tested by adding 700ppm of the process additive system to 35mL of corn syrup at 90 ℃ and then mixing for 0.5 minutes. Subsequently, 10mL of the treated slurry was transferred to a centrifuge tube and centrifuged at 3000rpm for 10 minutes. The amount of oil was determined by measuring the height of the oil layer in the centrifuge tube.

TABLE 14

As can be seen from table 14, the type of fatty acid methyl ester had no significant effect on the performance of the blends containing silica.

Example 15

The effect of the concentration of precipitated hydrophobic silica a and the presence and concentration of fumed hydrophobic silica (hydrophobic silica C) on the settling of the processing additive system was examined. The test was carried out by mixing 20g of a solution containing the specific components in Table 15 vigorously and then allowing it to stand for 5 weeks without disturbance. After that, the volume of settled was measured, divided by the total volume and reported as separation. Larger values indicate greater separation of the process additive system.

Watch 15

As can be seen from table 15, increasing the concentration of precipitated hydrophobic silica improves the settling stability of the process additive system. The addition of hydrophobic fumed silica increases the stability of the processing additive system, with higher concentrations yielding more stable processing additive systems.

Example 16

The effect of the concentration of hydrophobic silica on the viscosity of the processing additive system was examined. The viscosity was measured at room temperature (. about.24 ℃) using a Brookfield DV-II Pro viscometer equipped with a #6RV spindle at 50 RPM.

TABLE 16

As can be seen from table 16, varying the concentration of hydrophobic silica can be used to modify the viscosity of the processing additive system.

Example 17

The effect of the particle size of the hydrophobic silica on the viscosity of the processing additive system was investigated. The viscosity was measured at room temperature (. about.24 ℃) using a Brookfield DV-II Pro viscometer equipped with a #6RV spindle at 50 RPM.

TABLE 17

As can be seen from table 17, hydrophobic silicas having different particle sizes can be used to modify the viscosity of the processing additive system.

Example 18

The influence of the particle size of the added pyrogenic hydrophobic silicon dioxide on the viscosity of the processing additive system is examined. The viscosity was measured at room temperature (. about.24 ℃) using a Brookfield DV-II Pro viscometer equipped with a #6RV spindle at 50 RPM.

Watch 18

As can be seen from table 18, the addition of fumed hydrophobic silica can be used to modify the viscosity of the processing additive system.

Example 19

The influence of the addition of fatty acid methyl ester on the viscosity of the processing additive system is examined. The viscosity was measured at room temperature (. about.24 ℃) using a Brookfield DV-II Pro viscometer equipped with a #6RV spindle at 50 RPM.

Watch 19

As can be seen from table 19, the addition of fatty acid methyl esters can be used to modify the viscosity of the processing additive system.

Example 20

The effect of hydrophilic silica on the viscosity of the processing additive system was examined. A mixture containing about 13 wt% of hydrophilic silica having a particle size of 9 μm, about 1 wt% of methyl soyate, and 86 wt% of polysorbate 80 formed a gel that did not flow after the sample was inverted. This indicates that hydrophilic silica can modify the viscosity of the processing additive system.

Claims

1. A process for recovering oil from grain to ethanol production, the process comprising the step of adding a process additive system to a process stream, wherein the process additive system comprises at least one chemical additive and at least one hydrophobic silica having a particle size of at least 0.01 μm, wherein the total silica content of the process additive system is from 3 to 50 wt%, based on the weight of the process additive system, wherein the chemical additive comprises a functionalized polyol derived from sorbitol, sorbitan, isosorbide, sucrose, or glycerol.

2. The method of claim 1, wherein the functionalized polyol comprises at least one alkoxylated sorbitan alkylate.

3. The process of claim 2, wherein the alkylate has a chain length of 6-24 carbons or 8-18 carbons.

4. The method of claim 2 or 3, wherein the alkoxylated sorbitan alkylate has been alkoxylated with 5 to 60 moles of alkyl oxide or 10 to 30 moles of alkyl oxide or 12 to 25 moles of alkyl oxide.

5. The process of claim 4 wherein said alkyl oxide is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof.

6. The method of claim 2 or 3, wherein the alkoxylated sorbitan alkylate is selected from the group consisting of alkoxylated sorbitan monolaurate, alkoxylated sorbitan monooleate, alkoxylated sorbitan monopalmitate, alkoxylated sorbitan monostearate, and combinations thereof.

7. The method of claim 2 or 3, wherein the alkoxylated sorbitan alkylate comprises alkoxylated sorbitan monolaurate.

8. The method of claim 2 or 3, wherein the alkoxylated sorbitan alkylate comprises alkoxylated sorbitan monooleate.

9. The method of claim 1 or 2, wherein the hydrophobic silica has a median particle size of from 0.01 to 200 μm or from 0.01 to 100 μm or from 0.01 to 60 μm or from 0.1 to 200 μm or from 0.1 to 100 μm or from 0.1 to 60 μm or from 0.5 to 200 μm or from 0.5 to 100 μm or from 0.5 to 60 μm or from 1 to 200 μm or from 1 to 100 μm or from 1 to 60 μm.

10. The method of claim 1 or 2, wherein the hydrophobic silica comprises different particle sizes in the range of 0.01-200 μ ι η or 0.05-200 μ ι η or 0.1-100 μ ι η or 0.5-100 μ ι η.

11. The method of claim 1 or 2, further comprising the step of adding one or more modifiers to the process stream to adjust the settling stability, rheological properties, and/or elasticity of the process additive system.

12. The process of claim 1 or 2, wherein the total silica content is from 3 to 30 wt%, based on the weight of the process additive system.

13. The method of claim 1 or 2, wherein the total silica content is from greater than 5 wt% to 30 wt%, based on the weight of the process additive system.

14. The method of claim 11, wherein the modifying agent is selected from the group consisting of fatty acid alkyl esters, monoglycerides, diglycerides, triglycerides, mineral oils, alcohols, and combinations thereof.

15. The method of claim 11, wherein the modifying agent comprises fatty acid alkyl esters and/or triglycerides.

16. The method of claim 11, wherein the modifier is from 0.1 to 30 wt% based on the weight of the processing additive system, or from 0.1 to 25 wt% based on the weight of the processing additive system, or from 1 to 25 wt% based on the weight of the processing additive system.

17. The process of claim 1 or 2 wherein the amount of the process additive system added is from 20 to 10,000ppm based on the weight of the process stream, or from 20 to 4000ppm based on the weight of the process stream, or from 20 to 2000ppm based on the weight of the process stream, or from 20 to 1500ppm based on the weight of the process stream, or from 50 to 10,000ppm based on the weight of the process stream, or from 50 to 4000ppm based on the weight of the process stream, or from 50 to 2000ppm based on the weight of the process stream, or from 50 to 1500ppm based on the weight of the process stream, or from 100 + 10,000ppm based on the weight of the process stream, or from 100 + 4000ppm based on the weight of the process stream, or from 100 + 2000ppm based on the weight of the process stream, or from 100 + 1500ppm based on the weight of the process stream.

18. The method of claim 1 or 2, wherein the process additive system is heated to 18-100 ℃ or 25-85 ℃ or 30-80 ℃.

19. The method of claim 1 or 2, wherein the at least one addition point of the process additive system in the process stream is selected from the group consisting of a whole process stream prior to separation into wet cake and thin stillage, a process stream at or near the inlet of a centrifuge, or after the centrifuge, before or at the inlet and/or outlet of one or more thin stillage evaporators in an evaporator, thin stillage just before the centrifuge, an inlet to a premix or holdup heating tank, a point after a thin stillage addition tank and before a centrifuge, and combinations thereof.

20. The method of claim 1 or 2, wherein the process additive system is added to more than one addition point of the process stream.

21. The method of claim 1 or 2, wherein the cereal is corn.